Enhance Hydrogen Isotopes Separation by Alkali Earth Metal Dopant in Metal–Organic Framework

Kinetic quantum sieving (KQS) based on pore size and chemical affinity quantum sieving (CAQS) based on adsorption site are two routes of porous materials to separate hydrogen isotope mixtures. Alkali earth metals (Be, Mg, and Ca) were doped into UiO-67 to explore whether these metal sites can promote H₂/D₂ separation. Based on the zero-point energy and adsorption enthalpy calculated by density functional theory calculations, the Be dopant shows better H₂/D₂ separation performance than other alkali earth metal dopants and unsaturated metal sites in metal–organic frameworks based on CAQS. Orbital interaction strongly relates to the chemical affinity and further influences the D₂/H₂ selectivity. Moreover, the predicted D₂/H₂ selectivity of Be-doped sites (49.4) at 77 K is even larger than the best experimental result (26). Finally, the different dynamic behaviors of H₂ and D₂ on Be-doped UiO-67 indicate its strong H₂/D₂ separation performance via KQS.